JPH0139714B2 - - Google Patents

Abstract

@ An intumescent curable composition has as its principal constituents an epoxy resin; a curing agent; and an additive component which is composed of a mixture of materials which provide a source of phosphorus, zinc, boron, and an expansion gas. The aforesaid composition is capable of forming a carbonaceous char upon exposure to heat orflame.

Description

[Detailed description of the invention] Field of application of invention FIELD OF THE INVENTION The present invention relates to foamable flameproofing compositions.

BACKGROUND OF THE INVENTION The need to protect steel and concrete building structures, such as columns, beams, beams and other steel assemblies from damage from flames or high temperatures caused by fire, has recently been recognized. As a result, various flame retardant coating compositions have been developed and used for various applications. One application of particular interest is the protection of structural steel members and assemblies that remain exposed to climatic conditions. At one time, such structures were protected by the use of cementitious compositions. However, the use of cement presents a number of problems, such as the fact that cement is very heavy, or that cement has a strong tendency to absorb or retain water, resulting in corrosion of the steel. In recent years, intumescent flame retardant coating compositions have been investigated. Foamable flame retardant coating compositions are those that rapidly form insulating cellular carbonaceous chars when exposed to sufficient heat. For example, US Pat. No. 3,755,223 discloses epoxy resin-based intumescent flame retardant compositions. Many currently commercially available compositions are not without problems. For example, carbonaceous layers often crack and delaminate, leaving the substrate unprotected. To reduce these drawbacks, it is required to add reinforcing agents externally with the coating composition, but
As a result, prices will rise. moreover,
The composition may not expand uniformly, or may expand too little or too much during a fire, resulting in insufficient protection of the substrate. Also, typical intumescent flame retardant coating compositions tend to absorb water, causing corrosion of the internal steel. Therefore, when an intumescent flame-retardant coating composition comes into contact with flame or high temperatures, it forms a uniform char that adheres to the steel substrate without the addition of external reinforcing agents, and at the same time is able to withstand climatic conditions even in the absence of a fire. It is desirable to protect substrates from corrosion and other losses resulting from conditions.

Structure of the Invention The present invention provides: (a) an epoxy resin; (b) a curing agent for curing the epoxy resin; and (c) (i) phosphorus, (ii) zinc, (iii) boron, and (iv) expansion due to thermal decomposition. An additive component consisting of a mixture of gas-providing materials; an intumescent flame-retardant curable composition capable of forming a carbonaceous layer when exposed to heat or flame.

The present invention also provides: (a) an epoxy resin; (b) a curing agent for curing the epoxy resin; and (c) (i) phosphorus, (ii) zinc, (iii) boron, and (iv) generating an expanding gas by thermal decomposition. An additive component consisting of a mixture of substances to be supplied; a foamable flame-retardant curable composition coating capable of forming a carbonaceous layer when exposed to heat or flame is formed on the surface of the substrate; A method of protecting a substrate from fire or excessive temperatures by coating the flame retardant composition with a flame retardant composition is provided.

The foamable flameproof curable composition of the present invention contains an epoxy resin as a main component, a curing agent used for curing the epoxy resin, and additive components.

Epoxy resins have at least one oxirane group in their molecules, i.e. It refers to something that contains. It may have hydroxyl substituents and may also have halogen and ether groups. Generally, epoxy equivalent weights range from about 140 to about
1780, preferably 170-250, more preferably 185
~195. The resins may fall within the aliphatic, aromatic, cyclic, acyclic, alicyclic, or heterocyclic categories. Preferably, aromatic epoxy resin is used.

Particularly preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric aromatic alcohols, such as dihydric phenols. Phenols can be at least divalent; examples of suitable ones include resorcinol, catechol, hydroquinone, bis(4-hydroxyphenyl)-1,1-isobutane; 4,4-dihydroxybenzophenone; bis(4-hydroxyphenyl)-1,1-isobutane; -hydroxyphenyl)-1,1-ethane;
Bis(2-hydroxynaphenyl)methane; 1,
Mention may be made of 5-hydroxynaphthalene and 4,4'-isopropylidene diphenol, ie bisphenol A. Preference is given to using bisphenol A. Various epoxy compounds can be used.
What is used is epichlorohydrin,
Epibromohydrin is also very useful. Particularly useful polyglycyl ethers are obtained by reacting epichlorohydrin and bisphenol A in the presence of an alkali (eg, sodium or potassium hydroxide). Particularly useful are epoxy resins available from Shell Chemical Company under the Epon trademark.

Examples of other useful epoxy resins include polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, 1,
2-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,2,
6-hexanetriol, glycerol and trimethylolpropane).

Also useful are epoxy resins that are polyglycidyl ethers of polycarboxylic acids. For example, epoxy compounds (e.g. epichlorohydrin) and aliphatic or aromatic polycarboxylic acids (e.g. oxalic acid, succinic acid, glutaric acid, terephthalic acid,
2,6-naphthalene dicarboxylic acid and dimerized linolenic acid).

Other epoxy resins can also be obtained by epoxidizing olefinic unsaturated alicyclic substances. Epoxy cycloaliphatic ethers and esters are well known as examples of these.

Oxyalkylene group in addition to the above substances; [Wherein, R represents hydrogen or an alkyl group having 1 to 6 carbon atoms, m represents an integer of 1 to 4, and n represents an integer of 2 to 50. ] may be an epoxy resin containing. The above groups may be pendant groups to the epoxy resin backbone. It may also be included as part of the skeleton. The proportion of oxyalkylene groups in the epoxy resin varies depending on various factors, such as the size of the oxyalkylene groups and the nature of the epoxy resin.

Other epoxy resins include epoxy novolac resins. These resins are prepared by reacting condensates of aldehydes and mono- or polyhydric phenols with epihalohydrins. One example is the reaction product of epichlorohydrin and phenol formaldehyde condensate. Mixtures of epoxy resins may also be used.

The above epoxy resin requires the addition of a curing agent to impart thermosetting properties. Curing involves epoxy groups and (if present) hydroxy groups. Curing may occur at room temperature or elevated temperature. In general, curing agents used in the present invention may be selected from a variety of conventional materials, such as amine types including aliphatic or aromatic amines and poly(amine-amides). Examples of these are diethylenetriamine, 3,3-aminobispropylamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, and dienetriamine.
General Mills Chemicals
Inc.) as VERSAMID, a reaction product of an amine and an aliphatic fatty acid. Preferably poly(amine-amide) materials, e.g.
VERSAID or its equivalent is used.

Also suitable as curing agents are polycarboxylic acids and polycarboxylic anhydrides. Examples of polycarboxylic acids include di-, tri-, and higher carboxylic acids such as oxalic acid, phthalic acid, terephthalic acid, succinic acid, alkyl- and alkenyl-substituted succinic acid, tartaric acid, and polymerized fatty acids.
Examples of suitable polycarboxylic anhydrides include in particular pyromellitic anhydride, trimellitic anhydride,
Examples include phthalic anhydride, succinic anhydride, and maleic anhydride.

Also useful as curing agents are aldehyde condensation products such as urea-, melamine- or phenol-formterdehyde. These substances are commercially available under various names, such as from American Cyanamid.
BEETLE and CYMEL or Monsanto Industrial Chemical Co.
RESIMENE from Industrial Chemical Co.)
is exemplified.

Other suitable curing agents are boron trihalide and complexes of boron trihalide with amines, ethers, phenols, etc.; polymercaptans; polyphenols; metal salts such as aluminum chloride, zinc chloride and magnesium perchlorate; inorganic acids and partial esters. , such as phosphoric acid and orthophosphorous acid n
-Butyl etc. If desired, blocking or latent hardening agents may be used, such as ketimines prepared from polyamines and ketones.

Although the amounts of epoxy resin and curing agent used in preparing the intumescent mastic compositions of the present invention may vary, generally the epoxy to amine equivalent ratio will be within the range of 0.05:1 to 10:1. be. Preferably
0.1:1 to 1:1, more preferably 0.3:1 to 0.9:
It is within the range of 1.

The additive components of the mastic compositions of the present invention include phosphorus, zinc, boron and a mixture of materials that provide pyrolytic inflation gas. In a preferred embodiment, the additive component further contains a reinforcing filler.

The phosphorus source is selected from a variety of substances, such as phosphoric acid, mono- or diammonium phosphate, tris-(2-chloroethyl) phosphate, phosphorus-containing amides such as phosphorylamide and melamine pyrophosphate. Preferred phosphorous acid sources is an ammonium polyphosphate of the formula: (NH ₄ ) _o+2 P _o O _3o+1 where n is an integer of at least 2, preferably at least 50. Examples of the above substances include Monsanto Corporation
Commercially available as PHOS-CHEK-P-30 from
Alternatively, AMGAD from Albright and Wilson Corp.
Commercially available products are listed as IU. Preferably
Use PHOS-CHEK-P-30. The intumescent flame retardant compositions of the present invention typically contain from about 0.05 to about 20%, preferably from 0.5 to 10%, by weight of phosphorus (where % is the weight of the epoxy resin, curing agent, and additive components). (based on total weight). It is believed that phosphorus acts as a char accelerator in foamable flame retardant compositions.

The inflation gas is provided so that the flame retardant composition foams and expands, ie, foams, when exposed to high temperatures or flames. As a result of the expansion, the formed char becomes thick and porous so as to isolate and protect the core substrate. Preferably the source of inflation gas is a nitrogen-containing material. Examples of preferred nitrogen-containing materials include melamine, methylolated melamine, hexamethoxymethylmelamine, urea, dimethylurea, melamine pyrophosphate, dicyandiamide, guanylurea and glycine. Preferably melamine is used. Other conventional inflation gases may be, for example, carbon dioxide releasing substances. The additive amount of the inflation gas supply substance in the composition of the invention ranges from 0.1 to
25% by weight, preferably 1-10% by weight (in this case,
% is based on the total weight of epoxy resin, curing agent and additive components).

The zinc supply material can be selected from a variety of materials. It is believed that the zinc-providing material contributes to the formation of small cell structures within the char. The small cells of the char increase substrate isolation, preserve the integrity of the char, and improve adhesion to the substrate even without the presence of reinforcing agents. Thus, cracking and detachment of the chire from the substrate is reduced and greater protection of the underlying steel is provided. Examples of zinc sources include zinc oxide, zinc salts such as zinc borate and phosphate, zinc carbonate, and zinc metal may also be used. Preferably zinc oxide,
Zinc borate or zinc phosphate. The compositions of the invention usually contain 0.1 to 25% by weight of zinc, preferably 0.5 to 12% by weight. However, the above percentage is for epoxy resin,
Based on total amount of curing agent and additive components.

The boron-providing material is preferably boric acid, but
Various other materials may also be used. Boric acid acts as a fluxing acid that promotes uniform melting of the material when exposed to high temperatures or flames, contributing to the formation of a uniform char. Examples of suitable substances include boron oxide,
Mention may be made of borates such as sodium, potassium and ammonium borate, or borate esters such as butyl or phenyl borate. Boric acid is also preferred, followed by ammonium borate or sodium borate. Boron is present in the composition of the invention from 0.1 to 10
% by weight, preferably 1-6% by weight (% based on total amount of epoxy resin, curing agent and additive components)
contains.

Phosphorus, zinc, boron, and inflation gas may each be obtained from separate materials, or one material may provide one or more of the above elements. For example, melamine pyrophosphate provides both phosphorus and inflation gas.

The reinforcing filler, which is a preferred component of the additive component, may be selected from a variety of conventional types, such as fibrous and plate-like types. Fibrous and plate-like forms are preferred over others. Fibrous reinforcements include glass fibers, ceramic fibers (eg aluminum oxide/silicon oxide) and graphite fibers. Platy reinforcing agents include hammer mill glass flakes, mica, and wollastonite. Other suitable fillers include clay, talc, silica and various pigments. Preferably it is wollastonite. The reinforcing filler is believed to serve to control the expansion of the flame retardant composition prior to or during the formation of the char, thereby making the char stiff and uniform. If a reinforcing agent is used, it will usually be present in the composition at about 1
~50% by weight (% based on total weight of epoxy resin, curing agent and additive components).

The foamable flame retardant composition of the present invention is preferably a two-package system in which the epoxy resin is contained in a first package, the curing agent is contained in a second package, and the additive component is contained in either the first or second package, or both. It is. If additive components are included in both packages, each package may contain separate components, if desired. The two packages are mixed prior to use so that the epoxy to amine equivalent ratio of the final composition is within the above range. The compositions of the invention may be prepared as a single package system. In this case, the blocking or latent hardening agent is preferably, for example, the above-mentioned ketimine hardening agent. The ketimine curing agent is exposed to moisture as a result of the ketimine hydrolyzing, releasing free amine curing agent, and curing. Other latent hardeners, e.g. radiation
A material that releases a hardening agent as a result of exposure to water may also be used.

The compositions of the invention may also contain other conventional additives, such as stabilizers, rheology modifiers, fire spread control agents, and the like. The blending of these components is of course arbitrary, and the amounts added may vary widely.

The foamable flame retardant composition of the present invention is generally prepared in the form of a thick paste called mastic. Mastic can be applied by various methods, such as spray applicators and trowels. Preferably the composition of the invention is spray applied. Therefore, dilution of the mastic composition is generally necessary before application. Dilution is carried out using various conventional solvents, such as methylene chloride or 1,1,1-trichloroethane. A variety of conventional solvents are suitable, but preferably those that are non-flammable and have high volatility. The compositions of the present invention are particularly useful for application to steel substrates, but may also be used on other substrates, such as reinforced concrete, plastic, and wood.

In another embodiment of the present invention, (I) forming a film of the above-mentioned charge-forming foamable cured composition on the surface of the substrate;
() Provides a method of protecting a substrate from fire and excessive heat comprising coating the composition with a reticulated member. Preferably, the method may include the step of coating a mesh member with the intumescent flame retardant composition to substantially encapsulate the mesh member.

The mesh member may include a variety of mesh materials, such as wire mesh, or mesh formed from other refractory materials (eg, glass). The mesh is embedded within the mastic composition and is believed to inhibit expansion of the composition when exposed to heat or flame and prevent the formation of cracks within the formed chars. Furthermore, if a crack occurs, the mesh has a tearing part that prevents it from peeling off from the base material. This method is particularly useful for protecting steel substrates, especially those with flanged ends, grooves, and angles. In this method, another structural support member is provided to protect the char. Since the foamable flame retardant composition of the present invention adheres well to many substrates, there is no need to directly attach the substrate to the mesh member or to bond the mesh member to the substrate.

The intumescent flame retardant compositions of the present invention provide highly effective protection of structural steel or other assemblies from high temperatures or damage from flames. When the composition of the present invention is fired, a hard, small-celled char is formed that adheres to the substrate even in the absence of reinforcing agents;
Provide adequate isolation of buried steel. Even if a fire does not occur, the composition of the present invention can protect the substrate from e.g.
Effective protection against corrosion (the compositions of the invention prevent water absorption) and other damage resulting from climatic conditions.

The present invention will be explained in more detail with reference to Examples. The examples are intended to illustrate the invention and should not be construed as limiting.

Example 1 This example demonstrates the preparation and testing of a flame retardant foaming mastic composition of the present invention.

Ingredient weight parts (g) Package 1: EPON828 ¹ 35.77 Melamine 2.75 PHOS-CHEK-P-30 ²
4.52 Tall oil fatty acids 4.27 Tris (2-chloroethyl)
8.79 Phosphate ATTAGEL-50 ³ 3.31 Boric acid 20.64 Zinc borate 7.87 Wolastonite ⁴ 12.05 Package 2: VERSAMID150 ⁵ 72.25 AEROSIL200 ⁶ 3.50 IMSIL A-10 ⁷ 13.72 ATTAGEL-50 4.50 Talc 6.0 Carbon Black pigment 0.03 1 Bisphenol A and Epi Aromatic epoxy resin prepared from chlorohydrin. Epoxy equivalent
It has a solids content of 100% between 190 and 192. Shell
Commercially available from Chemical Company.

2 Ammonium polyphosphate with a phosphorus content of 32% by weight from Monsanto Corp.

3 Attapulgite clay used as a rheology modifier commercially available from Englehard minerals.

4 A fibrous reinforcing filler commercially available as NYAD G from Nycor Corp.

5 Amine curing agent with an average amine equivalent weight of 149 commercially available from General Mills Chemicals.

6 Humid silica used as a rheology modifier from Dugussa Corporation.

7 Amorphous silica commercially available from Illinois Minerals.

A mastic composition was prepared by mixing Package 1 (1.65 parts) and Package 2 (1 part). The mastic composition was applied to a 9 inch by 9 inch by 1/2 inch steel plate embedded with two thermocouples to form a uniform 3/10 inch thick coating on the top, bottom and sides. The plate was cured at room temperature for 2 days and passed ASTM-E119.
Fired in a gas furnace in accordance with (UL-263). The time required for the steel to reach a temperature of 1000㎓ (538℃) was measured. The test was stopped when the steel reached this temperature [this temperature was measured with each thermocouple]. When one or more thermocouples were used, the average value was used. However, each thermocouple is 1200〓
(649℃)].

The following data were obtained.

Thermocouple 1:55 to reach 1000〓(538℃):
51 (minutes: seconds).

Thermocouple 2: 56 to reach 1000〓 (538℃):
06.

The average value reached at the end of the test was 55:59.
The control plates were identical in all respects except that they were not coated with mastic composition. This unpainted 9" x 9" x 1/2" steel plate required 13 minutes to reach 1000°C (538°C).
The resulting chire is hard and exhibits excellent expandability.
It had small round cells.

EXAMPLE This example was prepared, coated, and oven tested in the same manner as Example I, except that zinc oxide was used in place of zinc borate.

Ingredient parts by weight (g) Package 1: EPON828 37.5 Melamine 2.8 PHOS-CHEK-P-30 4.8 Tall oil 4.5 Tris (2-chloroethyl)
9.2 Phosphate ATTAGEL-50 6.0 Boric acid 27.4 Wolastonite 6.5 Package 2: VERSAMID150 75.0 IMSIL A-10 14.7 AEROSIL200 3.0 Zinc oxide 7.3 A mastic composition was prepared in the same manner as in Example 1. Further, coating and testing were conducted in the same manner. The time it takes for the coating plate to reach 1000〓 (538℃) is
It was 65:41 (minutes: seconds).

Example A composition of the present invention was prepared, coated, and subjected to oven experiments in the same manner as in Example 2, except that zinc phosphate was used instead of zinc oxide.

Ingredient parts by weight (g) Package 1: EPON828 35.77 Melamine 2.75 PHOS-CHEK-P-30 4.52 Tall oil 4.27 Tris (2-chloroethyl)
8.79 Phosphate ATTAGEL 50 3.31 Boric acid 20.64 Zinc borate 7.87 Wollastonite 12.05 Package 2: VERSAMID150 75.0 AEROSIL200 3.0 Zinc phosphate 22.0 A mastic composition was prepared as in Example 1. 3 inches x 3 inches x with one thermocouple
Coating and testing was carried out as in Example I except that a 1/2 inch steel plate was used.

The painted steel plate took 44:10 (minutes:seconds) to reach 1000㎓ (538℃). The control plates were identical to the painted plates except that no mastic composition was applied. Unpainted 3 inch x 3 inch x 1/2 inch steel plate
It took 15 minutes to reach 1000〓 (538℃).

Example Using ammonium borate instead of boric acid,
The composition of the present invention was prepared, coated, and oven tested in the same manner as in Example I, except that RD-2 epoxy resin was newly used.

Ingredient parts by weight (g) Package 1: EPON828 420 RD-2 Epoxy ⁸ 17.3 Melamine 33.7 PHOS-CHEK-P-30 55.4 Tall oil 52.25 Tris (2-chloroethyl)
107.6 Phosphate ATTAGEL50 40.7 Ammonium borate 253 Zinc borate 97.8 Wollastonite 151.1 Package 2: VERSAMID150 705.29 AEROSIL200 28.18 IMSIL A-10 103.46 ATTAGEL-50 33.81 Talc 84.54 Carbon braz 0.30 8 1,4 commercially available from CIBA-GEIGY Corp. ―
Butanediol diglycidyl ether.

A mastic composition was prepared as in Example I,
3" x 3" x 1/2 with 1 thermocouple
Applied to inch steel plate. 1000〓
The time it took to reach (538°C) was 36:16 (minutes: seconds). The resulting char had a hard and small cell structure.

Example V A composition of the invention was prepared, coated and oven tested as in Example I, except that sodium borate was used in place of boric acid.

Ingredient parts by weight (g) Package 1: EPON828 35.77 Melamine 2.75 PHOS-CHEK-P-30 4.52 Tall oil fatty acid 4.27 Tris (2-chloroethyl)
8.79 Phosphate ATTAGEL 50 3.31 Sodium borate 20.64 Zinc borate 7.84 Wollastonite 12.05 Package 2: VERSAMID150 72.25 AEROSIL200 3.50 IMSIL A-10 13.72 ATTAGEL-50 4.50 Talc 6.0 Oil smoke pigment 0.03 The mastic composition of the present invention was prepared in the same manner as in Example 1. It was prepared and applied to a 3 inch x 3 inch x 1/2 inch steel plate with one thermocouple. 1000
〓It took 35:42 for the painted plate to reach (538℃)
It was (minutes: seconds). The resulting char is hard;
It also had a small cell structure.

EXAMPLE This example involved the preparation, application, and oven testing of a foamable flame retardant composition containing zinc borate, boric acid, and wollastonite. Packages 1 and 2 were mixed to obtain different epoxy to amine equivalent ratios from the previous examples. In addition, water resistance and absorbency were examined.

Component weight part (G) Patsukege 1: EPON828 47.1 melamine 2.6 Phos -Chek -30 4.3 Tol oil 4.0 ATTAGEL -50 3.2 Letjitin 0.24 octitine 0.24 donated zinc 7.50 Worse Night 11.00 Patsu Kage 2: VERSAMID150 56. 30 IMSIL A- 10 3.2 AEROSIL200 3.2 Tris (2-chloroethyl)
15.7 Phosphate Talc 9.6 ATTAGEL-50 3.8 Carbon Black Pigment 0.02 A mastic composition was prepared by mixing Package 1 (1.88 parts) and Package 2 (1 part). The mastic composition was applied to two 3 inch x 3 inch x 1/2 inch steel plates with one thermocouple as in the example.
Both plates were cured in two days. Then 2
One of the sheets (A) was baked as in Example I. the other
(B) was soaked in water at 180°C (82°C) for 4 days before baking.

Plate (A) is raised to 1000〓 (538℃)
It was 39:28. Cheer shows excellent foaming properties,
It had a small cell structure. No cracks occurred.

Plate (B) is raised to 1000〓 (538℃)
33:32 char has a small cell structure,
There were no cracks.

EXAMPLE This example illustrates the use of melamine pyrophosphate as a source of both phosphorus and inflation gas.

Ingredient parts by weight (g) Package 1: EPON828 35.77 Melamine pyrophosphate
7.27 Tall oil fatty acids 4.27 Tris(2-chloroethyl)
8.79 Phosphate ATTAGEL 50 3.31 Boric acid 7.87 Wolastonite 12.05 Zinc borate 7.87 Package 2: VERSAMID150 72.25 IMSIL A-10 13.72 AEROSIL200 3.50 ATTAGEL-50 4.50 Talc 4.50 Carbon black 0.30 A mastic composition was prepared as in Example I. Coated and tested as in Example I except that a 3 inch x 3 inch x 1/2 inch steel plate was used. Average time for painting plates is 36:38
(minutes: seconds).

Example A disaster prevention foaming mastic composition using cut glass fiber instead of wollastonite was obtained.

Ingredient parts by weight (g) Package 1: EPON828 37.94 Melamine 2.92 PHOS-CHEK-P-30 4.80 Tall oil 4.53 Tris (2-chloroethyl)
9.33 Phosphate boric acid 21.95 Zinc borate 8.48 ATTAGEL 50 3.53 Cut glass fiber (1/16 inch) 6.55 Package 2: VERSAMID150 73.83 IMSIL A-10 10.83 ATTAGEL-50 3.54 AEROSIL200 2.95 Talc 8.85 Mass A tick composition was prepared as in Example I. , applied and tested. The average time for coating steel plates was 49:24 (minutes:seconds). The resulting char was hard and had a small cell structure.

Example This example demonstrates the protection of substrates according to the invention.

A 4-foot 10W49 I-beam was coated with 3/10 inch of the disaster prevention foam mastic composition of the example. A cut fiber mat (commercially available as ABM mat from PPG Industries, Inc.) was placed over this coating. A further 3/10 inch of the above composition was applied onto the ABM mat. The beam was cured and fired as in Example I. As a control, the 4-ft.
A 10W49 I beam was coated with 6/10 inch of the above composition, but without a fiberglass mat. The control beam took 1 hour and 55 minutes to reach a temperature of 1000°C (538°C). 1000〓 (538
It took 2 hours and 10 minutes to reach the temperature (°C).

Although the present invention has been described with specific description and detailed examples, it is to be understood that modifications and substitutions made by those skilled in the art within the scope of the invention as set forth in the claims below are within the scope of the invention.

Claims (1)

[Scope of Claims] 1 (a) an epoxy resin; (b) a curing agent for curing the epoxy resin; and (c) (i) phosphorus, (ii) zinc, (iii) boron, and (iv) expanded by thermal decomposition. An intumescent flame retardant curable composition capable of forming a carbonaceous char when exposed to heat or flame, comprising: an additive component consisting of a mixture of gas supplying materials. 2. The composition according to item 1, wherein the additive component contains a reinforcing filler. 3. The composition according to item 2, wherein the epoxy resin is an aromatic epoxy resin. 4. The composition according to item 3, wherein the aromatic epoxy resin is a polyglycidyl ether of a polyhydric aromatic alcohol. 5. The composition according to item 4, wherein the epoxy resin is diglycidyl ether of 4,4'-isopropylidene diphenol. 6. The composition according to item 2, wherein the curing agent is a polyamine. 7. The composition of item 6, wherein the polyamine curing agent is a reaction product of an amine and an aliphatic fatty acid. 8 The phosphorus supply substance has the following formula; (NH ₄ ) _o+2 P _o O _3o+1 [wherein n represents an integer of at least 2]. ] The composition according to item 2, which is an ammonium polyphosphate represented by: 9. The composition of claim 8, wherein n is an integer of at least 50. 10 The second phosphorus-supplying substance is a phosphorus-containing amide
Compositions as described in Section. 11. The composition according to item 2, wherein the inflation gas supply substance is a nitrogen-containing substance. 12 No. 11 where the inflation gas supply material is melamine
Compositions as described in Section. 13. The composition of clause 2, wherein the zinc-providing substance is selected from the group consisting of zinc oxide, zinc borate, and zinc phosphate. 14. The composition of clause 2, wherein the boron-providing material is selected from the group consisting of boric acid, ammonium borate, and sodium borate. 15. The composition according to item 2, wherein the reinforcing filler is fibrous or plate-like. 16. The composition according to item 15, wherein the reinforcing filler is wollastonite. 17 The epoxy resin is in the first package, the curing agent is in the second package, and the additive is in the first or second package.
3. The composition according to item 2, which is a two-package system, which is incorporated into either or both of the packages. 18. The composition according to item 2, which is a one-package system using a latent curing agent as a curing agent. 19 (a) an epoxy resin; (b) a curing agent for curing the epoxy resin; and (c) a substance containing (i) phosphorus, (ii) zinc, (iii) boron, and (iv) a substance that provides expansion gas by thermal decomposition. A foamable flame-retardant curable composition film that can form a carbonaceous layer when exposed to heat or flame containing a mixture of additive components is formed on the surface of the substrate, and a mesh member is used to form the flame-retardant composition film. A method of protecting a substrate from flame or excessive temperatures by coating a composition. 20. The method according to paragraph 19, wherein the additive component is a reinforcing filler. 21. The method according to item 20, wherein the flame retardant composition coating is applied onto the mesh member so as to encapsulate substantially all of the mesh member. 22. The method according to item 20, wherein the epoxy resin is an aromatic epoxy resin. 23. The method according to item 20, wherein the curing agent is a polyamine. 24 The phosphorus supply substance has the following formula; (NH ₄ ) _o+2 P _o O _3o+1 [wherein n represents an integer of at least 2]. ] The method according to item 20, wherein the ammonium polyphosphate is represented by: 25. The method according to item 20, wherein the reinforcing filler is wollastonite. 26 Applying to the surface of a substrate a foamable flame-retardant curable composition that forms carbonaceous chars under flame conditions, retains its integrity, and is capable of adhering to the substrate without the addition of external reinforcing agents. , wherein the composition comprises (a) an epoxy resin; (b) a curing agent for curing the epoxy resin; and (c) (i) phosphorus, (ii) zinc, (iii) boron, and (iv) heat. an additive component consisting of a mixture of substances that provide inflation gas upon decomposition; and applying the composition to a 10W49 steel beam;
Approximately 0.6 inch thick and tested under Under-writer's Laboratories.
Laboratories test) UL-263,
A method of reducing the rate of temperature rise of a substrate under fire conditions in which the formed char can maintain the steel at a temperature below 1000 °C for at least about 2 hours. 27 No. 26 where the base material is architectural steel column
The method described in section.